CN101133116A - An improved low density ethylenic polymer composition and method of making the same - Google Patents
An improved low density ethylenic polymer composition and method of making the same Download PDFInfo
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- CN101133116A CN101133116A CN200680007050.6A CN200680007050A CN101133116A CN 101133116 A CN101133116 A CN 101133116A CN 200680007050 A CN200680007050 A CN 200680007050A CN 101133116 A CN101133116 A CN 101133116A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
Abstract
The instant invention is an improved low-density ethylenic polymer composition and method of making the same. The polymer composition according to instant invention includes a major component, and a minor component. The major component is an LDPE resin having a melt index (I2) in the range of about 0.01 dg/min to about 100 dg/min, a MW(abs)/MW(GPC) ratio of about 2.6 or less, and a melt strength of less than (14.0 e <(- i.o5*log10(MI))> )cN Jj16 mmor component is an LDPE resin having a melt index (I2) of less than about 5 dg/min, a molecular weight distribution of greater than about 7, and a MW(abs)/MW(GPC) ratio of at least 2.7. The polymer composition of the instant invention may further include additional components. Furthermore, the free radical initiation polymerization process according to instant invention includes the following steps: providing ethylene; and reacting the ethylene in a reactor system, which includes at least one tubular reactor and at least one autoclave reactor, at a high pressure range of about 18,000 psig to about 55,000 psig, at a reactor temperature of about 190 DEG C to about 400 DEG C, wherein the ethylene feed into the reactors is divided into multiple ethylene feed streams, and at least one of the ethylene feed streams into the tubular reactor consists essentially of the unreacted ethylene. Additionally, the free radical initiation polymerization process according to instant invention may further include the steps of providing at least one or more comonomers; and reacting the ethylene and the comonomer(s) in the reactor system a a high pressure range of about 18,000 psig to about 55,000 psig, at a reactor temperature of about 190 DEG C to about 400 DEG C.
Description
Invention field
The present invention relates to improved low density ethylenic (ethylenic) polymer composition and manufacture method thereof.
The cross reference of related application
The application requires the U.S. Provisional Application series No.60/658 of " the LOW DENSITYETHYLENIC POLYMERIC COMPOSITIONS WITH IMPROVEDPROCESSIBILITY " by name of submission on March 4th, 2005, it just looks like to repeat fully hereinafter equally that 962 right of priority, the content of its instruction are incorporated herein by this reference.
Background of invention
Is known by polyethylene (" PE ") resin through melting and spraying membrane process (being also referred to as bubble method) manufacturing film.In meltblown, because it has limited film production rate, bubble stability is an important factor.In addition, the bubble stability resin is directly connected to melt strength (" MS ").
Be well known that equally hp-ldpe (" LDPE ") innately has than the higher melt strength of linear polyethylene (" LPE ").Therefore, LDPE is particularly useful for blowing the thick gauge bubbles of major diameter.
The production of LDPE be can promote by different methods, autoclave method (autoclave process) or tubular process included but not limited to.Although autoclave LDPE resin may have high fondant-strength, the film made of resinoid does not show and the identical tenacity levels of being made by melt index (" MI ") the tubular type LDPE resin identical with autoclave LDPE resin of film thus.In addition, can provide the conversion of ethylene higher although produce this LDPE resin than autoclave method through tubular process (promptly using tubular reactor); But in order to reach the melt strength identical with autoclave resin, the melt index of tubular type resin is compared with autoclave resin and must significantly be reduced; Therefore, throughput rate is caused negative impact thereupon.
The open No.0069806A1 of European patent discloses the poly method that a kind of manufacturing has stable physics and chemical property.
U.S. Provisional Application No.60/624,434 disclose a kind of method of low-density polyethylene composition and polymkeric substance of making thus made.
Although in exploitation with improve and to study aspect the high fondant-strength resin, still need to have the resin of the high fondant-strength of suitable high-throughput film production.
Summary of the invention
The present invention is improved low density ethylenic polymer composition and manufacture method thereof.Polymer composition of the present invention comprises main component and submember.Main component is melt index (I
2) be that about 0.01dg/min is to about 100dg/min, M
W (abs)/ M
W (GPC)Than for about 2.6 or lower and melt strength be lower than (14.0e
(1.05*log10 (MI))) the LDPE resin of cN.Submember is melt index (I
2) being lower than about 5dg/min, molecular weight distribution is greater than about 7 and M
W (abs)/ M
W (GPC)Than the LDPE resin that is at least 2.7.Polymer composition of the present invention may further include supplementary component.In addition, free radical polymerization method of the present invention comprises the following steps: to provide ethene; In the reactor assembly that comprises at least one tubular reactor and at least one autoclave reactor, about 18,000psig is to about 55, under the high pressure of 000psig, to about 400 ℃ temperature of reactor, make ethylene reaction at about 190 ℃, the ethene that wherein enters in the reactor is divided into the multiply ethylene feed stream, and one ethylene feed stream at least that enters in the tubular reactor is made of unreacted ethene substantially.In addition, free radical polymerization method of the present invention may further include provides at least a or multiple comonomer; With in this reactor assembly, about 18,000psig is to about 55, under the high pressure of 000psig, in about 190 ℃ of steps that make ethene and the reaction of this comonomer to about 400 ℃ temperature of reactor.
Detailed Description Of The Invention
The present invention relates to improved low density ethylenic polymer composition and manufacture method thereof.
Following term has given implication for purposes of the invention:
Melt strength used herein is meant at it by the standard plastometer, for example during the plastometer described in the ASTMD1238-E at it more than fusing point, traction (haul-off) the speed stretching that reached before causing disconnected speed under stablizing with melt strength melt extrudes required stress of thing or power (applying by the coiling drum of being furnished with strainometer)
Polymkeric substance used herein is to instigate the monomer polymerization of identical or different type and the macromolecular compound made.Therefore the technical term polymkeric substance comprises term " homopolymer ", and it is meant the polymkeric substance of only being made by one type monomer, and " multipolymer ", and it is meant the polymkeric substance of being made by two or more different monomers.
Term " LDPE " (being also referred to as " high pressure ethylene polymer ", " high pressure low density type resin " or " highly branched polyethylene ") be meant polymkeric substance in autoclave or tubular reactor, be higher than 14, under the pressure of 500psi (100MPa), by the radical initiator of superoxide and so on partially or completely homopolymerization or copolymerization (referring to for example US 4,599,392, it is incorporated herein by this reference).
Term used herein " line style PE " or " LPE " be meant any line style, substantial linear or heterogeneous polyethylene and ethylene copolymers or homopolymer.Line style PE can be by any method preparation, for example vapor phase process, molten liquid phase method or slurry process or its combination.Line style PE can be made of one or more compositions, and its each also is line style PE.
Term used herein " molecular weight distribution " or " MWD " are meant weight-average molecular weight (M
w) and number-average molecular weight (M
n) ratio, i.e. (M
w/ M
n).
M used herein
W (abs)/ M
W (GPC)Ratio is meant M
W (abs)With M
W (GPC)Ratio; M wherein
W (abs)Be the weight-average molecular weight of releasing by the injection volume of scattering of light area under the low angle (as 15 degree) and polymkeric substance, M
W (GPC)It is the weight-average molecular weight that obtains by the GPC calibration.The alignment light scatter detector produces the weight-average molecular weight suitable with the GPC instrument with the linear polyethylene homopolymer standard substance for NBS 1475 and so on.
Low-density polymer composition of the present invention comprises main component and submember.
Main component can be any polyolefine.Main component is ethene polymers preferably, for example hp-ldpe (" LDPE ").Main component can have any melt index (I
2); For example, main component preferably has about 0.01 to about 100dg/min melt index (I
2).Main component more preferably has about 0.1 to about 5.0dg/min, most preferably about 0.2 to about 2.0dg/min melt index (I
2).Main component can have any melt strength; For example, main component can have and is lower than (14.0e
(1.05*log10 (MI))) melt strength of cN.Main component can have any M
W (abs)/ M
W (GPC)Ratio; For example, main component can have and is lower than 2.6 M
W (abs)/ M
W (GPC)Ratio.Main component can have any density; For example, main component can have about 0.917 to about 0.935 gram per centimeter
3Density.
Submember can be any polyolefine.Submember is ethene polymers preferably, for example hp-ldpe (" LDPE ").Submember can have any melt index (I
2); For example, submember can have the melt index that is lower than about 5.0dg/min.Submember preferably has about 0.1 to about 2.0dg/min melt index (I
2); More preferably about 0.2 to about 1.0dg/min melt index (I
2); Most preferably about 0.2 to about 0.7dg/min melt index (I
2).Submember can have any molecular weight distribution (" MWD "); For example, submember preferably can have the molecular weight distribution greater than 7.Submember more preferably has the molecular weight distribution greater than 10.Submember can have any M
W (abs)/ M
W (GPC)Ratio; For example, submember can have at least 2.7 M
W (abs)/ M
W (GPC)Ratio.Submember preferably can have the M greater than 3
W (abs)/ M
W (GPC)Ratio; Submember most preferably has the M greater than 3.5
W (abs)/ M
W (GPC)Ratio.Submember can have any density; For example, submember can have about 0.917 to about 0.935 gram per centimeter
3Density.
Polymer composition of the present invention can contain about 1 submember to about 49 weight % that accounts for main and submember gross weight.This polymer composition preferably contains about 3 submembers to about 25 weight % that account for main and submember gross weight; This polymer composition most preferably contains about 5 submembers to about 15 weight % that account for main and submember gross weight.In addition, this polymer composition can contain about 1 to about 100 weight % the main and submember that accounts for polymer composition weight, and its remainder can be any other supplementary component as described below.This polymer composition can have any melt index (I
2); For example, this polymer composition preferably has about melt index of 0.01 to about 100.0dg/min; More preferably about 0.1 to about 10.0dg/min melt index (I
2).This polymer composition can have any melt strength; For example, this polymer composition can have (the 14.0e greater than f*
(1.05*log10 (MI))) melt strength; F=1 wherein, preferred f=1.1, most preferably f=1.2; Wherein MI is the melt index (I of this polymer composition
2).This polymer composition can have any M
W (abs)/ M
W (GPC)Ratio; For example, this polymer composition preferably has greater than { 1.2+ (7 (M
w/ 10
6)) M
W (abs)/ M
W (GPC)Ratio.This polymer composition can have any molecular weight distribution (MWD); For example, this polymer composition preferably has less than { 3.0+ (4 (M
w/ 10
5)) molecular weight distribution.This polymer composition can have any density; For example, this polymer composition can have about 0.86 to about 0.96 density; Or this polymer composition can have about 0.917 to about 0.935 gram per centimeter
3Density.
This polymer composition may further include supplementary component, include but not limited to, antioxidant, surface slip agent, anti-hard caking agent (antiblock agent), ultra-violet stabilizer, additive, natural polymer, synthetic polymer, for example linear polyethylene polymkeric substance, substantially linear polyethylene, even branching linear ethylene polymer composition, heterogeneous branched ethylene polymer and blend thereof.In U.S. Patent No. 5,272, further discussed the substantially linear polyethylene polymkeric substance in 236,5,278,272,5,582,923 and 5,733,155.In U.S. Patent No. 3,645, further discussed even branching linear ethylene polymer composition in 992.In U.S. Patent No. 4,076, further discussed heterogeneous branched ethylene polymer in 698,3,914,342 and 5,854,045.Can pass through gas phase, solution phase or slurry polymerization process or their any combination, use the reactor or the reactor structure of any kind known in the art to make this LPE, and it can pass through any method known in the art modification, for example uses electron beam, superoxide coupling, oxygen adjustment (tailoring) or the like to improve melt strength.
Aborning, can make polymer composition of the present invention, for example by blending, parallel reactor and series connection autoclave-tubular reactor by the whole bag of tricks.
Can make polymer composition of the present invention by blending.Hybrid system is normally known.Usually, composition independently, promptly main component and submember can be made separately, mix subsequently to make polymer composition of the present invention.
Perhaps, can make polymer composition of the present invention by parallel reactor.The use of parallel reactor is known.Usually, composition independently, promptly main component and submember are made simultaneously by parallel reactor, and reduce the back blending at reactor pressure and form polymer composition of the present invention.
Again or, can make polymer composition of the present invention by placed in-line autoclave-tubular reactor.Can have placed in-line one or more autoclave-tubular reactor.Describe present method with single autoclave-tubular reactor, still, present method is not limited to single autoclave-tubular reactor, for example, can have a plurality of placed in-line autoclave-tubular reactors.When using single autoclave-tubular reactor, this method preferably includes the free radical polymerization method.This free radical polymerization method can comprise the following steps: to provide ethene; In the reactor assembly that comprises at least one tubular reactor and at least one autoclave reactor, about 18,000psig is to about 55, under the high pressure of 000psig, make ethylene reaction to about 400 ℃ temperature of reactor at about 190 ℃, the ethene that wherein enters in the reactor is divided into the multiply ethylene feed stream, and one ethylene feed stream at least that enters in the tubular reactor is made of unreacted ethene substantially.In addition, free radical polymerization method of the present invention further comprises provides at least a or multiple comonomer; With make ethene and this comonomer in reactor assembly, about 18,000psig is to about 55, under the high pressure of 000psig, in about 190 ℃ of steps of reacting to about 400 ℃ temperature of reactor.Temperature of reactor is preferably about 200 ℃ to about 350 ℃, and more preferably about 210 ℃ to about 320 ℃, most preferably about 220 ℃ to about 300 ℃.Autoclave and tubular reactor preferably with this order series operation, wherein are diverted to maximum ethylene feed stream in the tubular reactor by y=1-(0.35)
xDetermine; Wherein the y representative enters the maximum feed mark (maximum fractional feed) in the tubular reactor, and the x representative enters the sum of the ethylene feed stream in the tubular reactor.Per share ethylene feed stream preferably remains below under the temperature of temperature of reactor.The temperature of tubular reactor can reach at least 250 ℃ peak temperature behind each injection radical initiator.Tubular reactor peak temperature used herein is meant the maximum temperature that reaches at this tubular reactor after injecting radical initiator.Preferably make polymer composition of the present invention by shunting ethylene feed between autoclave reactor and tubular reactor.But, also all ethylene feed can be introduced in the autoclave reactor and be made polymer composition of the present invention.This ethylene feed of shunting helps to control better the molecular weight distribution of given weight molecular weight resin between autoclave reactor and tubular reactor.Because autoclave reactor can move under any temperature, the shunting ethylene feed helps the optimization of melt strength, long chain branching, molecular weight distribution, rheological, density and total conversion rate between autoclave reactor and tubular reactor, helps the required transformation efficiency between the realization response device to share simultaneously.Because it helps to control independently the molecular weight distribution under the given molecular weight, the shunting of ethylene feed helps to produce and has the more polymer composition of high fondant-strength and long chain branching, makes quite most polymer composition simultaneously in the tubular reactor section of autoclave-tubular reactor structure.Therefore, this method is particularly suitable for being manufactured on the resin that has wide especially molecular weight distribution under the given molecular weight.In addition, it is more favourable than blending method to use autoclave-tubular reactor to make polymer composition of the present invention, because this method helps to eliminate the needs of handling various kinds of resin and the extrusion condition that may cause gel to generate.
As mentioned above, can also make polymer composition of the present invention, so that the average reactor temperature minimally of autoclave is observed functional expression Y=(0.006P+85) by autoclave-tubular reactor; Wherein Y is the average autoclave temperature of reactor with ℃ expression, and P is the autoclave reactor pressure of representing with psig.Determine average autoclave temperature of reactor according to following equation: average autoclave temperature of reactor=∑ (weight fraction of making under Ti) (Ti); Wherein Ti is the maximum temperature among the conversion zone i, and i is at least 1.
In addition, also can make polymer composition of the present invention by aforesaid autoclave-tubular reactor under following condition: F is more than or equal to (0.021*Y
2)-((9.48*Y)+1318); F=((X*Z)+((1-X) * Y), and the wherein mark of all polymkeric substance of in tubular reactor, transforming of X representative, the wherein maximum temperature of reactor that reaches in the tubular reactor of Z representative with ℃ expression wherein.
In use, it is the purposes or the method for advantage that polymer composition of the present invention can be used for any melt strength that improves down with given melt index, includes but not limited to cast film and blown film, thermoforming, blowing, foam manufacturing, extrusion coated.
The high fondant-strength autoclave resin can be added among the tubular process LDPE of melt index with certain limit, the selection of this melt index depend on end-use with obtain for shrinkable film (～0.7MI), general purpose film (～2.0MI), transparent film (～2.0MI) and so on purposes and the higher throughput rate of other purposes.Usually with converter (converter) with LDPE and linear polyethylene (LPE) blending to improve the physical properties of made final film.The gained blend has lower maximum processing speed---and this compares relatively low melt strength owing to LPE (line style or substantially linear polyethylene) usually with LDPE.Thus by the novel LDPE that shows higher bubble unstable initiation conditions is provided, the present invention makes converter compare with the level that otherwise may reach can to mix more LPE and/or moves with higher rate.Aspect autoclave-tubular type of the present invention, the resin of making can have tubular type resin any melt index commonly used, but have the melt strength of raising, further mix with the LPE that the amount that allows than prior art is Duoed thereby the ability of moving with higher rate is provided and/or helps.In another aspect of this invention, the LDPE of minor amount can be added among the LPE to improve the processing speed of LPE---this is reduced to cost (tear strength, anti-piercing through property, mechanical bruise resistance or the like) with the LPE physical properties usually; Therefore, it is favourable providing the LDPE of the ability with higher stable LPE film bubble; Therefore, need sneak into less LDPE, provide the deterioration of physicals to compare low final mixture before thus.Can select converter using and the LPDE of same amount before, and realize with compare before higher throughput rate, still less LDPE and realize the better physical performance, or realize both combinations.
Testing method
Testing method comprises as follows:
Measure the melt strength values of representing with centi-Newtons (cN) with G ttfert Rheotens.With air gap, promptly by the distance of die head exit, be made as 100 millimeters to reel, the wheel acceleration is 2.4 mm/second
2Unless make separate stipulations,, make melt down at 190 ℃ with the piston speed of 0.265 mm/second by being furnished with 12 millimeters machine barrels and G ttfert Rheotester 2000 with die head (L=30 millimeter, ID=2 millimeter) of flat inlet.
According to ASTM D792 test density.
Measure melt index according to ISO 1133:1997 or ASTM D1238:1999 down at 190 ℃; With 2.16 kilograms of weight measurement I
2Numerical value is represented with gram/10 minutes or dg/min.
Use traditional GPC to measure weight-average molecular weight (M according to method well known in the art
w) and number-average molecular weight (M
n).
Adopt gel permeation chromatography " GPC " as described below to record MWD and M
W (abs)/ M
W (GPC)Ratio:
(Amhest, MA) (Millford, MA) 150C high temperature chromatographic instrument constitutes the Waters of two angle laser light scattering detector models 2040 this chromatographic system by being furnished with Precision Detectors.Use 15 degree angles of light scattering detector to calculate molecular weight.(Houston, TX) TriSEC software the 3rd edition and 4-passage Viscotek Data Manager DM400 carry out data gathering to use Viscotek.This system is equipped with (Shropshire, online solvent degasser UK) from Polymer Laboratories.
Carousel compartment (carousel compartment) is 140 ℃ of operations, and column compartment is 150 ℃ of operations.Used post is a 7Polymer Laboratories 20-micron Mixed-A LS post.Solvent for use is 1,2,4 trichlorobenzene.Prepared at concentrations sample with 50 milliliters of solvents, 0.1 gram polymkeric substance.Chromatographic solvent and sample preparation solvent contain 200ppm Yoshinox BHT (BHT).Two kinds of solvent source are all used nitrogen purging.With polyethylene specimen 160 ℃ of mild stirring 4 hours.Used injection volume is that 200 microlitres and flow velocity are 1.0 ml/min.
The calibration molecular weight of GPC column device is 580 to 8,400, and 18 narrow molecular weight distributions polystyrene standards of 000 are carried out, and they are arranged on 5 and differ between the molecular weight separately in decimal at least " cocktail " mixture.Standard substance available from Polymer Laboratories (Shropshire, UK).For being equal to or greater than 1,000,000 molecular weight with 0.025 gram in 50 milliliters of solvents, for less than 1,000,000 molecular weight prepares polystyrene standards with 0.05 gram in 50 milliliters of solvents.Polystyrene standards was dissolved down in mild stirring at 80 ℃ in 30 minutes.At first use narrow standard substance mixture, and the highest weight component is successively decreased so that minimum degradation.Use following formula (as Williams and Ward, J.Polym.Sci., Polym.Let. is described in 6,621 (1968)) that the polystyrene standards peak molecular weight is changed into molecular weight of polyethylene:
M
Polyethylene=A * (M
Polystyrene)
B
Wherein M is a molecular weight; A has 0.41 value, and B equals 1.0.Use each polyethylene of quartic polynomial match-equivalent setting point.
The master plate of GPC column device counting (total plate count) with Eicosane (with 0.04 gram in 50 milliliters of TCB preparation and under mild stirring, dissolved 20 minutes) carry out.Measure plate count and symmetry according to following formula with 200 microlitre injection volumes:
Plate count=(5.54) (RV/ under peak-peak (peak width at half height)) ^2
Wherein RV is the retention volume of representing with milliliter, and peak width is represented with milliliter.
Symmetry=(at the back of the body peak width under 1/10 height-)/(at the preceding peak width of the RV-under the peak-peak under 1/10 height) at the RV under the peak-peak
Wherein RV is the retention volume of representing with milliliter, and peak width is represented with milliliter.
According to Balke, people such as Mourey (Mourey and Balke, ChromatographyPolym.Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym.Chpt 13, (1992)) mode of disclosed unanimity is used to measure the Systematization method of multi-detector skew (multi-detector off-set), use carry (in-house) software will be from the dual-detector log MW result optimizing of the wide polystyrene 1683 of Dow to narrow standard column calibration result from narrow standard substance working curve.According to Zimm (Zimm, B.H., J.Chem.Phys., 16,1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)) mode of disclosed unanimity obtains molecular weight data.The total injection concentration that is used for determining molecular weight is available from sample refractive index zone and the refractive index detector calibration undertaken by the linear polyethylene homopolymer of 115,000 molecular weight.Suppose that chromatographic concentrations is enough low to eliminate addressing secondary Virial coefficient effect (concentration is to the influence of molecular weight).
In order to monitor deviation in time, it can contain elution component (being caused by the chromatogram variation) and velocity component (being caused by the pump variation), uses the back narrow peak conduct of wash-out " marker peak " usually.Therefore set up flow marker (flow tate marker) based on degassing chromatographic system solvent and the air peak mismatch (mismatch) between the elution samples on one of vinylbenzene cocktail mixture.By the calibration of air peak, use the flow velocity of flow marker linear calibration all samples.Any variation of supposing the marker peak time then is relevant with the linear displacement of flow velocity and chromatogram slope.
For the pinpoint accuracy that the retention volume (RV) that promotes flow marker peak is measured, use least squares fitting to come flow marker peak according to quadratic equation match concentration chromatogram.Use the first order derivative of quadratic equation to solve actual peak position then.After calibrating this system, as formula 1, calculate effective liquidate speed (as the measurement of calibration slope) based on flow marker peak.In high temperature SEC system, can use antioxidant mismatch peak or air peak (if moving phase fully outgases) as the effective liquidate speed mark.The principal character of effective liquidate speed mark is as follows: flow marker should singly be disperseed.Flow marker (flow marker) should with total post permeation volume wash-out closely.Flow marker should disturbed specimen chromatographic integration window.
Formula 1
Effective liquidate speed=(nominal flow rate) (flow marker calibration/observed flow marker)
Preferred column device has 20 micron granularities and " mixing " porosity that is enough to separate the highest weight cut that meets claim.
By the low angle (less than 20 degree) of on NBS 1476 hp-ldpe standard substance, watching online light scattering detector, can examine competent post and separate and suitable shearing rate.Suitable scattering of light color atlas should show bimodal (high MW peak and the moderate molecular weight peak) with roughly suitable peak height.By confirming between two peaks, to have half the trough height that is lower than total LS peak height, should just have competent separation.The plate count of chromatographic system (based on aforesaid eicosane) should be higher than 32,000, and symmetry should be 1.00 to 1.12.
Embodiment
The present invention of the following example illustration, but be not to limit the scope of the invention.
Used resin (MI=I among the embodiment
2, dg/min):
R1:LDPE 203M (Dow)-0.3MI, 0.921g/cc (tubular type LDPE)
R2:LDPE 662i (Dow)-0.47MI, 0.918g/cc (autoclave LDPE:
M
W (abs)/ M
W (GPC)Than=3.7; MWD=9.1)
R3：DOWLEX NG 2085B(Dow)-0.85MI，0.920g/cc(LPE)
R4:LDPE 204M (Dow)-0.3MI, 0.921g/cc (tubular type LDPE)
R5：DOWLEX 2045(Dow)-1.0MI，0.920g/cc(LPE)
R6:LDPE 132i (Dow)-0.22MI, 0.921g/cc (tubular type LDPE:MS=20cN;
M
W (abs)/ M
W (GPC)Than=2.28)
White/black MB is the pigment in the LPE of MI=20 base
Embodiment 1-2: prove the effectiveness of the present invention in the major diameter that is used for agriculture silage film, thick specification, multilayer high-throughput commercial use.
Every layer resin mixes by dry mix, and compound in being extruded into the process of die head.
Coextruded structure A/B/C (33/34/33); Film thickness=238 micron (9.4 mil); Die head=142.2 centimetre (56 inches); BUR=2.0.
A:R1 (32%)+R2 (5%)+R3 (55%)+white MB (8%)
B:R1 (32%)+R2 (5%)+R3 (56%)+white MB (7%)
C:R1 (35%)+R2 (5%)+R3 (52%)+black MB (8%)
Example 1: maximum output=1000 kilogram/hour.
Comparative Examples 2: (surplus is mended flat by increasing R1) maximum output=960 kilogram/hour under the situation of not using R2.
Embodiment 3-4: prove the effectiveness of the present invention in the major diameter that is used for agriculture silage film, thick specification, multilayer high-throughput commercial use.
Every layer resin mixes by dry mix, and compound in being extruded into the process of die head.
Coextruded structure A/B/C (33/34/33); Die diameter=1.2 meter (3.9ft); Vesicle diameter=2.77 meter (9ft), 228 microns of thickness (gauge) (9.0 mil).
A:R4 (62%)+R2 (8%)+R3 (18%)+white MB (12%)
B:R4 (65%)+R2 (8%)+R3 (19%)+white MB (8%)
C:R4 (52%)+R2 (8%)+R3 (30%)+black MB (10%)
Example 3: with 900 kilograms/hour throughput rate operation.
Comparative Examples 4:%R2=0, surplus is mended flat by increasing %R4; Owing to, can not realize 900 kilograms/hour throughput rate reaching 900 kilograms of/hour cephacoria bubble collapsings.
When not having R2 (surplus is mended flat by increasing R4), film bubble collapsing under required throughput rate.Use R2, generate stable bubble.
Embodiment 5-10: prove in small scale laboratory equipment exist and do not exist LPE as ternary situation under effectiveness of the present invention.A kind of statement of bubble instability is " venting (breathing) ", and the folding of film footpath (layflat) and specification thereupon change thus.As the reduction of comparing folding footpath (layflat) difference with the non-embodiment of the invention that does not contain high fondant-strength LDPE (resin R2), measure effect of the present invention.Experimentize, minimize and use extremely low blow-up ratio (BUR), produce film bubble with maximum specification possible on this equipment by making the maximization of forcing machine throughput rate, derivation speed.Under these conditions, need (chilled) cooling air stream of height Quench to realize stable film bubble.In equipment used, need be under 45 the flow velocity of 93cu ft/min.Realized under the situation of stable bubble airflow being reduced to 58cu ft/min in this condition of use, and after 5 minutes, measured the variation of folding footpath.Need regular time, improve in time until the film follicular rupture usually because the folding footpath changes.These embodiment show that composition of the present invention is effective especially in the presence of LPE.
Single layer structure.If desired, resin dry is mixed and is compound in extrusion.
Forcing machine: 2 inch diameters, L/D=24: 1, melt temperature=444 ;
Die diameter=3 inch; Die gap=70mil; BUR=1.35; Throughput rate=56lb/hr; Derive speed=18ft/min;
Use 58 cubic feet/min, the Quench airflow of temperature=45-50 is measured the folding footpath and is changed.
| Embodiment | Blend is formed | The folding footpath changes (inch) | ||||
| ％R5 | ％R2 | ％R6 | Maximum | Minimum | Difference | |
| Comparative Examples 5 | 0 | 0 | 100 | 7.75 | 4.75 | 3 |
| Example 6 | 0 | 5 | 95 | 7.375 | 5.125 | 2.25 |
| Example 7 | 0 | 20 | 80 | 7 | 5.625 | 1.375 |
| Comparative Examples 8 | 20 | 0 | 80 | 6.5 | 5.5 | 1 |
| Example 9 | 20 | 5 | 75 | 6.785 | 6 | 0.785 |
| Example 10 | 20 | 10 | 70 | 6.625 | 6.125 | 0.5 |
Claims (27)
1. composition comprises:
Main component, wherein said main component contains melt index (I
2) scope is about 0.01dg/min to approximately 100dg/min, M
W (abs)/ M
W (GPC)Than for about 2.6 or lower and melt strength be lower than (14.0e
(1.05*log10 (MI))) the LDPE resin of cN; With
Submember, wherein said submember contains melt index (I
2) be lower than about 5dg/min, molecular weight distribution greater than about 7 and M
W (abs)/ M
W (GPC)Than the LDPE resin that is at least 2.7.
2. according to the composition of claim 1, wherein said submember has the melt index (I of about 0.1dg/min to about 2.5dg/min
2) and greater than about 3.0 M
W (abs)/ M
W (GPC)Ratio.
3. according to the composition of claim 1, wherein said submember has about 0.2dg/min to the melt index of about 1.0dg/min with greater than about 3.5 M
W (abs)/ M
W (GPC)Ratio.
4. according to the composition of claim 1, wherein said composition comprises about 1 submember to about 49 weight % that accounts for described main and submember gross weight.
5. according to the composition of claim 4, wherein said composition comprises about 5 submembers to about 30 weight % that account for described main and submember gross weight.
6. according to the composition of claim 4, wherein said composition comprises about 10 submembers to about 25 weight % that account for described main and submember gross weight.
7. according to the composition of claim 1, wherein said composition comprises approximately at least 1 to about 100 weight % the described main and submember that accounts for described composition total weight.
8. according to the composition of claim 1, the melt strength of wherein said composition is greater than (1.1) (14.0e
(1.05*log10 (MI))) cN.
9. according to the composition of claim 1, the melt strength of wherein said composition is greater than (1.2) (14.0e
(1.05*log10 (MI))) cN.
10. according to the composition of claim 1, wherein said composition further contains linear polyethylene.
11. comprise the composition of LDPE resin, wherein said composition has the melt index (I of about 0.01dg/min to about 100dg/min
2), greater than (14.0e
(1.05*log10 (MI))) cN melt strength and greater than 1.2+ (7*M
w/ 10
6) M
W (abs)/ M
W (GPC)Ratio.
12. according to the composition of claim 11, the melt index (I of wherein said composition
2) be that about 0.1dg/min is to about 10dg/min.
13. according to the composition of claim 11, wherein the melt strength of said composition is greater than (1.1) (14.0e
(1.05*log10 (MI))) cN.
14. according to the composition of claim 11, wherein the melt strength of said composition is greater than (1.2) (14.0e
(1.05*log10 (MI))) cN.
15. a free radical polymerization method comprises the following steps:
Ethene is provided;
In comprising the reactor assembly of at least one tubular reactor and at least one autoclave reactor, about 18,000psig under the high pressure of 000psig, makes ethylene reaction at about 190 ℃ to about 55 to about 400 ℃ temperature of reactor;
The ethene that wherein enters in the reactor is divided into the multiply ethylene feed stream, and one the described ethylene feed stream at least that enters in the described tubular reactor is made of unreacted ethene substantially.
16. according to the free radical polymerization method of claim 15, wherein said method further comprises step:
At least a or multiple comonomer is provided; With
In this reactor assembly, about 18,000psig under the high pressure of 000psig, makes ethene and the reaction of this comonomer at about 190 ℃ to about 55 to about 400 ℃ temperature of reactor.
17. according to each free radical polymerization method of claim 15-16, wherein said temperature of reactor is about 200 ℃ to about 350 ℃.
18. according to each free radical polymerization method of claim 15-16, wherein said temperature of reactor is about 210 ℃ to about 320 ℃.
19. according to each free radical polymerization method of claim 15-16, wherein said temperature of reactor is about 220 ℃ to about 300 ℃.
20. according to each free radical polymerization method of claim 17-19, wherein autoclave and tubular reactor be with this order series operation, is diverted to maximum ethylene feed stream in the tubular reactor by y=1-(0.35)
xDetermine that wherein the y representative enters the maximum feed mark in the tubular reactor, the x representative enters the sum of the ethylene feed stream in the tubular reactor.
21. according to the free radical polymerization method of claim 20, wherein the temperature of per share described ethylene feed stream all is lower than temperature of reactor.
22. according to each described free radical polymerization method of claim 15-21, wherein the average reactor temperature minimally of autoclave is observed functional expression Y=(0.006P+85); Wherein Y is the average autoclave temperature of reactor with ℃ expression, and P is the autoclave reactor pressure of representing with psig.
23., wherein inject the peak temperature that pipe reaction actuator temperature behind the radical initiator has at least 250 ℃ at every turn according to the free radical polymerization method of claim 22.
24. according to the free radical polymerization method of claim 23, wherein F 〉=(0.021*Y
2)-(9.48*Y)+(1318), wherein F=(X*Z)+((1-X) * Y)), wherein X represents the mark of the polymkeric substance total amount that transforms in pipe, the maximum temperature of reactor with ℃ expression that the Z representative reaches in tubular reactor.
25. according to the composition that the method for claim 24 is made, wherein said composition comprises the LDPE resin, and wherein said composition has the melt index (I of about 0.01dg/min to about 100dg/min
2), greater than (14.0e
(1.05*log10 (MI))) cN melt strength, greater than 1.2+ (7*M
w)/10
6M
W (abs)/ M
W (GPC)Than and less than 3.0+ (4*M
w)/10
5MWD.
26. goods comprise:
A kind of polymer composition, it comprises:
Main component, wherein said first composition is melt index (I
2) be that about 0.01dg/min is to about 100dg/min, M
W (abs)/ M
W (GPC)Than for about 2.6 or lower and melt strength be lower than (14.0e
(1.05*log10 (MI))) the LDPE resin of cN; With
Submember, wherein said second composition is melt index (I
2) be lower than about 5dg/min, molecular weight distribution greater than about 7 and M
W (abs)/ M
W (GPC)Than the LDPE resin that is at least 2.7.
27. goods comprise:
A kind of polymer composition that comprises the LDPE resin, wherein said polymer composition have the melt index (I of about 0.01dg/min to about 100dg/min
2), greater than (14.0e
(1.05*log10 (MI))) cN melt strength and greater than 1.2+ (7*M
w/ 10
6) M
W (abs)/ M
W (GPC)Ratio; And less than about 3.0+ (4*M
w/ 10
5) MWD.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410529772.4A CN104356460B (en) | 2005-03-04 | 2006-03-03 | improved low density ethylenic polymer composition and its manufacturing method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US65896205P | 2005-03-04 | 2005-03-04 | |
| US60/658,962 | 2005-03-04 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410529772.4A Division CN104356460B (en) | 2005-03-04 | 2006-03-03 | improved low density ethylenic polymer composition and its manufacturing method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101133116A true CN101133116A (en) | 2008-02-27 |
Family
ID=36584916
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680007050.6A Pending CN101133116A (en) | 2005-03-04 | 2006-03-03 | An improved low density ethylenic polymer composition and method of making the same |
| CN201410529772.4A Active CN104356460B (en) | 2005-03-04 | 2006-03-03 | improved low density ethylenic polymer composition and its manufacturing method |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Country Status (12)
| Country | Link |
|---|---|
| US (1) | US7863386B2 (en) |
| EP (1) | EP1858973B1 (en) |
| JP (1) | JP5179199B2 (en) |
| CN (2) | CN101133116A (en) |
| AR (1) | AR054011A1 (en) |
| BR (1) | BRPI0608052A2 (en) |
| CA (1) | CA2598450C (en) |
| ES (1) | ES2531982T3 (en) |
| MX (1) | MX2007010792A (en) |
| NO (1) | NO20074435L (en) |
| SG (1) | SG160354A1 (en) |
| WO (1) | WO2006096504A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917591A (en) * | 2011-10-31 | 2014-07-09 | 东洋制罐集团控股株式会社 | Polyethylene resin composition, and container using same |
| CN104371048A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | High melting index and low density polyethylene for ultrafine fiber leather |
| CN105143337A (en) * | 2013-05-01 | 2015-12-09 | 陶氏环球技术有限责任公司 | Low density ethylene-based polymer compositions with good melt strength and high density |
| CN114989340A (en) * | 2022-06-28 | 2022-09-02 | 杭州双安科技有限公司 | Olefin polymerization method |
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| RU2444546C2 (en) | 2006-04-07 | 2012-03-10 | ДАУ ГЛОБАЛ ТЕКНОЛОДЖИЗ ЭлЭлСи | Polyolefin compositions, articles made therefrom and preparation methods thereof |
| ATE483753T1 (en) | 2008-05-19 | 2010-10-15 | Borealis Tech Oy | EXTRUSION COATING OF A POLYETHYLENE COMPOSITION |
| US8679639B2 (en) | 2009-11-24 | 2014-03-25 | Dow Global Technologies Llc | Extrusion coating composition |
| US8784996B2 (en) | 2009-11-24 | 2014-07-22 | Dow Global Technologies Llc | Extrusion coating composition |
| ES2604339T3 (en) | 2011-11-23 | 2017-03-06 | Dow Global Technologies Llc | Low density ethylene-based polymers with wide molecular weight distributions and low level of extractable substances |
| EP2782960B1 (en) | 2011-11-23 | 2016-11-09 | Dow Global Technologies LLC | Low density ethylene-based polymers with extracts at lower molecular weights |
| CN105189637B (en) * | 2013-05-22 | 2018-02-06 | 陶氏环球技术有限责任公司 | Composition containing tool high molten intensity low density ethylene based polyalcohol and the film formed by it |
| ES2868951T3 (en) * | 2013-05-22 | 2021-10-22 | Dow Global Technologies Llc | Low-density ethylene-based polymer compositions with high melt strength and medium-high density control |
| ES2838748T3 (en) | 2013-05-22 | 2021-07-02 | Dow Global Technologies Llc | Low-density ethylene-based compositions with improved melt strength, yield, and mechanical properties |
| US9828495B2 (en) * | 2014-12-19 | 2017-11-28 | Dow Global Technologies Llc | Low haze polyethylene polymer compositions |
| WO2016178768A1 (en) * | 2015-05-07 | 2016-11-10 | Exxonmobil Chemical Patents Inc. | Hygiene articles and processes for making the same |
| WO2017106940A1 (en) * | 2015-12-22 | 2017-06-29 | Braskem S.A. | Device for injecting a polymerization initiator in a tubular reactor, tubular reactor for continuous polymerization of olefins, and process for producing ethylene copolymers and polymers |
| JP7279300B2 (en) * | 2017-03-28 | 2023-05-23 | 東ソー株式会社 | Resin composition and film made of the same |
| KR102145496B1 (en) | 2018-11-29 | 2020-08-18 | 롯데케미칼 주식회사 | Low density polyethylene resin with ecellent processability and preparation method thereof |
| AR119441A1 (en) * | 2019-07-31 | 2021-12-15 | Dow Global Technologies Llc | LOW DENSITY POLYETHYLENE WITH IMPROVED HOT BOND STRENGTH AND ADHESION TO METAL THROUGH THE ADDITION OF IONOMERS |
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-
2006
- 2006-03-03 ES ES06748279.4T patent/ES2531982T3/en active Active
- 2006-03-03 BR BRPI0608052-9A patent/BRPI0608052A2/en active IP Right Grant
- 2006-03-03 SG SG201001459-5A patent/SG160354A1/en unknown
- 2006-03-03 CN CN200680007050.6A patent/CN101133116A/en active Pending
- 2006-03-03 EP EP06748279.4A patent/EP1858973B1/en active Active
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- 2006-03-03 US US11/817,231 patent/US7863386B2/en active Active
- 2006-03-03 JP JP2007558263A patent/JP5179199B2/en active Active
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103917591A (en) * | 2011-10-31 | 2014-07-09 | 东洋制罐集团控股株式会社 | Polyethylene resin composition, and container using same |
| CN103917591B (en) * | 2011-10-31 | 2016-02-24 | 东洋制罐集团控股株式会社 | Polyethylene resin composition and the container using it |
| US9475926B2 (en) | 2011-10-31 | 2016-10-25 | Toyo Seikan Group Holdings, Ltd. | Polyethylene resin composition and containers using the same |
| CN105143337A (en) * | 2013-05-01 | 2015-12-09 | 陶氏环球技术有限责任公司 | Low density ethylene-based polymer compositions with good melt strength and high density |
| CN104371048A (en) * | 2013-08-13 | 2015-02-25 | 中国石油化工股份有限公司 | High melting index and low density polyethylene for ultrafine fiber leather |
| CN104371048B (en) * | 2013-08-13 | 2018-01-19 | 中国石油化工股份有限公司 | A kind of high melt index and low density polyethylene for super fiber leather |
| CN114989340A (en) * | 2022-06-28 | 2022-09-02 | 杭州双安科技有限公司 | Olefin polymerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| US20080255302A1 (en) | 2008-10-16 |
| WO2006096504A1 (en) | 2006-09-14 |
| MX2007010792A (en) | 2007-09-26 |
| SG160354A1 (en) | 2010-04-29 |
| US7863386B2 (en) | 2011-01-04 |
| BRPI0608052A2 (en) | 2009-11-03 |
| NO20074435L (en) | 2007-12-03 |
| EP1858973B1 (en) | 2014-12-31 |
| CA2598450C (en) | 2013-07-02 |
| CN104356460A (en) | 2015-02-18 |
| JP5179199B2 (en) | 2013-04-10 |
| AR054011A1 (en) | 2007-05-30 |
| JP2008531831A (en) | 2008-08-14 |
| ES2531982T3 (en) | 2015-03-23 |
| EP1858973A1 (en) | 2007-11-28 |
| CN104356460B (en) | 2018-11-20 |
| CA2598450A1 (en) | 2006-09-14 |
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